Thiopheneazo dyes with a coupling component based on m-phenylenediamine

ABSTRACT

Thiopheneazo dyes of the formula ##STR1## where X is cyano or C 1  -C 4  -alkoxycarbonyl, 
     Y is halogen, hydroxyl, mercapto, substituted or unsubstituted C 1  -C 6  -alkoxy, C 5  -C 7  -cycloalkoxy, substituted or unsubstituted phenoxy, substituted or unsubstituted C 1  -C 6  -alkylthio, C 5  -C 7  -cycloalkylthio, substituted or unsubstituted phenylthio, C 1  -C 6  -alkylsulfonyl or substituted or unsubstituted phenylsulfonyl, 
     Z is nitro, cyano, C 1  -C 4  -alkanoyl, benzoyl, C 1  -C 4  -alkylsulfonyl, phenylsulfonyl or a radical of the formula --CH═CB 1  B 2  or --CH═N--B 3 , in which B 1  and B 2  independently of the other are cyano, substituted or unsubstituted C 1  -C 6  -alkoxycarbonyl or C 3  -C 6  -alkenyloxycarbonyl or one of B 1  and B 2  is cyano and the other is C 1  -C 4  -alkylsulfonyl, substituted or unsubstituted phenyl, benzoyl, phenylsulfonyl or carbamoyl and B 3  is hydroxyl, C 1  -C 4  -alkoxy, phenoxy or phenylamino, 
     R 1  is C 1  -C 4  -alkoxy, 
     R 2  is hydrogen, substituted or unsubstituted C 1  -C 10  -alkyl or R 3 , 
     R 3  is a radical of the formula CH 2  --CH(OR 5 )--CH 2  R 6  and 
     R 4  is substituted or unsubstituted C 1  -C 6  -alkanoylamino or substituted or unsubstituted benzoylamino, 
     R 5  being hydrogen, C 1  -C 10  -alkanoyl, C 1  -C 10  -alkoxycarbonyl or C 1  -C 10  -mono- or -dialkyl-carbamoyl, the alkyl groups of said substituents being uninterrupted or interrupted by oxygen atoms, and 
     R 6  being chlorine, bromine hydroxyl or substituted or unsubstituted 
     are useful for dyeing textile fibers.

The present invention relates to novel thiopheneazo dyes of the formulaI ##STR2## where

X is cyano or C₁ -C₄ -alkoxycarbonyl,

Y is halogen, hydroxyl, mercapto, unsubstituted or phenyl-substituted C₁-C₆ -alkoxy, C₅ -C₇ -cycloalkoxy, substituted or unsubstituted phenoxyunsubstituted or phenyl-substituted C₁ -C₆ -alkylthio, C₅ -C₇-cycloalkylthio, substituted or unsubstituted phenylthio, C₁ -C₆-alkylsulfonyl or substituted or unsubstituted phenylsulfonyl,

Z is nitro, cyano, C₁ -C₄ -alkanoyl benzoyl C₁ -C₄ -alkylsulfonyl,phenylsulfonyl or a radical of the formula --CH═CB¹ B² or --CH═N--B³, inwhich B¹ and B² are identical or different and each independently of theother are cyano, C₁ -C₆ -alkoxycarbonyl whose alkyl chain may beinterrupted by one or more oxygen atoms, or C₃ -C₆ -alkenyloxycarbonylor one of B¹ and B² is cyano and the other is C₁ -C₄ -alkylsulfonylsubstituted or unsubstituted phenyl, benzoyl, phenylsulfonyl orcarbamoyl and B³ is hydroxyl-, C₁ -C₄ -alkoxy, phenoxy or phenylamino,

R¹ is C₁ -C₄ -alkoxy,

R² is hydrogen, C₁ -C₁₀ -alkyl which may be interrupted by one or moreoxygen atoms, or R³,

R³ is a radical of the formula CH₂ --CH(OR⁵)--CH₂ R⁶ and

R⁴ is unsubstituted or hydroxyl-, C₁ -C₄ -alkoxy-, phenoxy-, chlorine-or C₁ -C₄ -alkanoyloxy-substituted C₁ -C₆ -alkanoylamino or substitutedor unsubstituted benzoylamino,

R⁵ being hydrogen, C₁ -C₁₀ -alkanoyl, C₁ -C₁₀ -alkoxycarbonyl or C₁ -C₁₀-mono- or -dialkyl-carbamoyl, the alkyl groups of said substituentsbeing uninterrupted or interrupted by one or more oxygen atoms, and

R⁶ being chlorine, bromine, hydroxyl, phenoxy, allyloxy, C₁ -C₁₀ -alkoxywhich may be interrupted by one or more oxygen atoms or substituted byhydroxyl phenoxy, phenyl, C₁ -C₈ -alkanoyloxy, chlorine, bromine orcyano, C₁ -C₆ -alkanoyloxy, C₁ -C₆ -mono- or -dialkylaminocarbonyloxy orphenylaminocarbonyloxy.

EP-A-201,896, DE-A-3,529,831 and DE-A-3,535,133 already disclosethiopheneazo dyes of a similar structure.

It is an object of the present invention to make available newthiopheneazo dyes which have a coupling component based onm-phenylenediamine and which have advantageous application properties.

We have found that this object is achieved by the thiopheneazo dyes ofthe formula I specified at the beginning.

All the alkyl and alkenyl groups appearing in the abovementionedradicals can be not only straight-chain but also branched.

If substituted phenyl appears in the abovementioned formula I, suitablesubstituents are for example C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or halogen,in particular chlorine or bromine.

Oxygen-interrupted alkyl in the abovementioned formula I is preferablyinterrupted by one or two oxygen atoms.

Z in the formula I is for example formyl, acetyl, propionyl, butyryl orisobutyryl.

X, B¹ and B² are for example methoxycarbonyl, ethoxycarbonyl,propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl orisobutoxycarbonyl.

B¹ and B² are each further for example pentyloxycarbonyl,isopentyloxycarbonyl, neopentyloxycarbonyl, hexyloxycarbonyl,2-methoxyethoxycarbonyl, 2-ethoxyethoxycarbonyl, 2-butoxyethoxycarbonyl,allyloxycarbonyl, methallyloxycarbonyl, ethylallyloxycarbonyl, phenyl,4-methylphenyl, 2-ethoxyphenyl, 4-chlorophenyl or 2,4-dichlorophenyl.

B¹ and B², like Y and Z, are each further for example methylsulfonyl,ethylsulfonyl, propylsulfonyl, isopropylsulfonyl or butylsulfonyl.

Y is further for example fluorine, chlorine, bromine, methoxy, ethoxy,propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, pentyloxy,isopentyloxy, neopentyloxy, tert-pentyloxy, hexyloxy, benzyloxy,2-phenylethoxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, phenoxy,4-methylphenoxy, 4-isopropylphenoxy, 4-methoxyphenoxy, 4-bromophenoxy,methylthio, ethylthio, isopropylthio, benzylthio, 2-phenylethylthio,cyclohexylthio, phenylthio, 4-chlorophenylthio, pentylsulfonyl,isopentylsulfonyl, hexylsulfonyl or 4-methylphenylsulfonyl.

R¹ and B³ are each for example methoxy, ethoxy, propoxy, isopropoxy,butoxy, isobutoxy or sec-butoxy.

R² is for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl,sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl,heptyl, octyl, 2-ethylhexyl, nonyl, decyl, 2-methoxy-ethyl,2-ethoxyethyl, 2-propoxyethyl, 2-butoxyethyl, 2-methoxypropyl,3-methoxypropyl, 3-ethoxypropyl, 2-methoxybutyl, 4-methoxybutyl,2-ethoxybutyl, 4-ethoxybutyl, 3,6-dioxaheptyl or 3,6-dioxaoctyl.

R⁴ is for example NHCOCH₃, NHCOC₂ H₅, NHCOC₃ H₇, NHCOCH₂ OCH₃, NHCOCH₂OC₂ H₅, NHCOCH₂ OC₆ H₅, NHCOCH₂ OH, NHCOCH₂ OCOCH₃, NHCOCH₂ Cl, NHCOC₂H₄ OCH₃, NHCO₆ H₅, NHCOC₆ H₄ -4-OCH₃, NHCOC₆ H₄ -4-CH₃ or NHCOC₆ H₄-4-Cl.

R⁵ is for example formyl, acetyl, propionyl, butyryl, isobutyryl,pentanoyl, isopentanoyl, hexanoyl, heptanoyl, octanoyl, 2-ethylhexanoyl,nonanoyl, decanoyl, 4-oxapentanol, 4-oxahexanoyl, 4,7-dioxaoctanoyl,methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl,isopropoxycarbonyl, isobutoxycarbonyl, pentyloxycarbonyl,hexyloxycarbonyl, mono- or dimethylcarbamoyl, mono- or diethylcarbamoyl,mono- or dipropylcarbamoyl, mono- or diisopropylcarbamoyl or mono- ordibutylcarbamoyl.

R⁶ is not only as defined above but also for example methoxy, ethoxy,propoxy, isopropoxy, butoxy, isobutoxy, pentyloxy, hexyloxy, heptyloxy,octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, 2-methoxyethoxy,2-ethoxyethoxy, 2-propoxyethoxy, 2-butoxyethoxy, 2-methoxypropoxy,3-methoxypropoxy, 3-ethoxypropoxy, 2-methoxybutoxy, 4-methoxybutoxy,2-ethoxybutoxy, 4-ethoxybutoxy, 3,6-dioxaheptyloxy, 3,6-dioxaoctyloxy,2-phenylethoxy, 8-phenyl-4,7-dioxaoctyloxy, 2-cyanoethoxy,2-cyanopropoxy, 3-cyanopropoxy, 4-cyanobutoxy, 5-cyano-3-oxapentyloxy,6-cyano-4-oxahexyloxy, 8-cyano-4-oxahexyloxy, 2-hydroxyethoxy, 2- or3-hydroxypropoxy, 2,3-dihydroxypropoxy, 2-hydroxybutoxy,4-hydroxybutoxy,5-hydroxy-3-oxapentyloxy, 6-hydroxy-4-oxahexyloxy,8-hydroxy-4-oxaoctyloxy, 8-hydroxy-3,6-dioxaoctyloxy,2-phenyl-2-hydroxethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-phenoxyethoxy,3-phenoxypropoxy, 4-phenoxybutoxy, 5-phenoxy-3-oxapentyloxy,6-phenoxy-4-oxahexyloxy, 8-phenoxy-4-oxaoctyloxy,2-formyloxyethoxy,2-acetyloxyethoxy, 2-propionyloxyethoxy, 2-butyryloxyethoxy,2-(2-ethylhexanoyloxy)ethoxy, 2- or 3-acetyloxypropoxy, 2- or3-propionyloxypropoxy, 2- or 3-(2-ethylhexanoyloxy)propoxy,4-acetyloxybutoxy, 4-propionyloxybutoxy, 4-(2-ethylhexanoyloxy)butoxy,5-acetyloxy-3-oxapentyloxy, 5-propionyloxy-3-oxapentyloxy,5-(2-ethylhexanoyloxy)-3-oxapentyloxy, 6-acetyloxy-4-oxahexyloxy,6-propionyloxy-4-oxahexyloxy, 6-(2-ethylhexanoyloxy)-4-oxahexyloxy,8-acetyloxy-4-oxaoctyloxy, 8-propionyloxy-4-oxaoctyloxy,8-(2-ethylhexanoyloxy)-4-oxaoctyloxy, formyloxy, acetyloxy,propionyloxy, butyryloxy, isobutyryloxy, pentanoyloxy, hexanoyloxy,mono- or dimethylcarbamoyloxy, mono- or diethylcarbamoyloxy, mono- ordipropylcarbamoyloxy, mono- or diisopropylcarbamoyloxy, mono- ordibutylcarbamoyloxy or N-methyl-N-ethylcarbamoyloxy.

Preference is given to thiopheneazo dyes of the formula I where

X is cyano or C₁ -C₄ -alkoxycarbonyl,

Y is halogen, C₁ -C₄ -alkoxy, phenylthio or phenylsulfonyl,

Z is cyano, formyl or a radical of the formula --CH═CB¹ B², in which B¹is cyano and B² is cyano or C₁ -C₄ -alkoxycarbonyl,

R¹ is C₁ -C₄ -alkoxy,

R² is hydrogen or C₁ -C₄ -alkyl,

R³ is a radical of the formula --CH₂ --CH(OR⁵)--CH₂ R⁶ and

R⁴ is C₁ -C₄ -alkanoylamino,

R⁵ being hydrogen or C₁ -C₄ -alkanoyl and

R⁶ being chlorine bromine hydroxy, phenoxy, allyloxy, C₁ -C₄ -alkoxy orC₁ -C₄ -alkanoyloxy.

Particular preference is given to thiopheneazo dyes of the formula Iwhere

X is cyano,

Y is chlorine, bromine, methoxy, ethoxy, phenylthio or phenylsulfonyl,

Z is cyano or formyl,

R¹ is methoxy or ethoxy,

R² is hydrogen or C₁ -C₄ -alkyl,

R³ is a radical of the formula --CH₂ --CH(OR⁵)--CH₂ R⁶ and

R⁴ is C₁ -C₄ -alkanoylamino,

R⁵ being hydrogen or C₁ -C₄ -alkanoyl and

R⁶ being chlorine, bromine, hydroxy, phenoxy, allyloxy, C₁ -C₄ -alkoxyor C₁ -C₄ -alkanoyloxy.

Suitable dyes are in particular those of the formula I where

X is cyano,

Y is chlorine or ethoxy,

Z is cyano or formyl,

R² is hydrogen,

R⁴ is acetylamino and

R⁵ is hydrogen.

The thiopheneazo dyes of the formula I according to the presentinvention can be prepared in a conventional manner. For instance, anaminothiophene of the formula II ##STR3## where X, Y and Z are each asdefined above, can be diazotized and coupled to an m-phenylenediaminederivative of the formula III ##STR4## where R¹, R², R³ and R⁴ are eachas defined above.

The aminothiophenes II and m-phenylene derivatives III are in generalknown compounds (for example see EP-A-193,885 and also DE-A-3,004,654).

The novel thiopheneazo dyes are advantageously used as disperse dyes fordyeing textile fibers, in particular polyesters or cellulose esters, butalso polyamides or blend fabrics of polyesters and cellulose fibers.They have not only a high color strength but also very good fastnessproperties.

The Examples which follow will illustrate the invention in more detail.

EXAMPLE 1

9.4 g of 2-amino-4-chloro-5-formyl-3-cyanothiophene were suspended atnot more than 30° C. in 60 ml of 85% strength by weight sulfuric acid.16.6 g of nitrosylsulfuric acid (11.5% of N₂ O₃) were added dropwise at0°-5° C. over 0.5 hours, and the mixture was stirred at that temperaturefor a further 2 hours.

The diazonium salt solution thus obtained was slowly run at 0°-5° C.into a mixture of 16 g ofN-(2-hydroxy-4-oxaoctyl)-2-methoxy-5-acetylaminoaniline in 25 ml ofN,N-dimethylformamide, 100 ml of water, 20 ml of dilute hydrochloricacid, 0.5 g of sulfamic acid and 300 g of ice. After the coupling hadended, the dye was filtered off with suction, washed neutral and dried.This gave 20.9 g of the dye of the formula ##STR5## which dyes polyesterfibers in fast, greenish blue shades.

The same method was used to obtain the dyes of the formula ##STR6##listed in Table 1.

                                      TABLE 1                                     __________________________________________________________________________    Ex.                                                                           No.                                                                              X  Y Z   R.sup.1                                                                           R.sup.2                                                                          R.sup.4  R.sup.5                                                                         R.sup.6 Hue on PES                              __________________________________________________________________________     2 CN Cl                                                                              CHO OCH.sub.3                                                                         H  NHCOC.sub.2 H.sub.5                                                                    H OC.sub.2 H.sub.5                                                                      greenish                                                                      blue                                     3 CN Cl                                                                              CHO OC.sub.2 H.sub.5                                                                  H  NHCOCH.sub.3                                                                           H OC.sub.4 H.sub.9                                                                      greenish                                                                      blue                                     4 CN Cl                                                                              CHO OCH.sub.3                                                                         H  NHCOCH.sub.3                                                                           H OCH.sub.3                                                                             greenish                                                                      blue                                     5 CN Cl                                                                              CHO OCH.sub.3                                                                         H  NHCOCH.sub.3                                                                           H OC.sub.6 H.sub.5                                                                      greenish                                                                      blue                                     6 CN Cl                                                                              CHO OCH.sub.3                                                                         H  NHCOCH.sub.3                                                                           H OH      greenish                                                                      blue                                     7 CN Cl                                                                              CHO OCH.sub.3                                                                         H  NHCOCH.sub.3                                                                           H OC.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                     greenish                                                                      blue                                     8 CN Cl                                                                              CHO OCH.sub.3                                                                         H  NHCOCH.sub.3                                                                           H OCH.sub.3                                                                             greenish                                                                      blue                                     9 CN Br                                                                              CHO OCH.sub.3                                                                         H  NHCOCH.sub.3                                                                           H OC.sub.4 H.sub.9                                                                      greenish                                                                      blue                                    10 CN Cl                                                                              CHO OC.sub.2 H.sub.5                                                                  H  NHCOC.sub.2 H.sub.5                                                                    H OC.sub.4 H.sub.9                                                                      greenish                                                                      blue                                    11 CN Cl                                                                              CHO OCH.sub.3                                                                         H  NHCOC.sub.2 H.sub.5                                                                    H OC.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                     greenish                                                                      blue                                    12 CN Cl                                                                              CHO OCH.sub.3                                                                         H  NHCOCH.sub.2 OCH.sub.3                                                                 H OH      greenish                                                                      blue                                    13 CN Cl                                                                              CHO OCH.sub.3                                                                         H  NHCOC.sub.6 H.sub.5                                                                    H OC.sub.4 H.sub.9                                                                      greenish                                                                      blue                                    14 CN Cl                                                                              CHO OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                  NHCOCH.sub.3                                                                           H OC.sub.4 H.sub.9                                                                      greenish                                                                      blue                                    15 CN Cl                                                                              CHO OCH.sub.3                                                                         C.sub.4 H.sub.9                                                                  NHCOCH.sub.3                                                                           H OC.sub.2 H.sub.5                                                                      greenish                                                                      blue                                    16 CN Cl                                                                              1)  OCH.sub.3                                                                         H  NHCOCH.sub.3                                                                           H OC.sub.4 H.sub.9                                                                      green                                   17 CN Cl                                                                              2)  OCH.sub.3                                                                         H  NHCOCH.sub.3                                                                           H OC.sub.4 H.sub.9                                                                      green                                   18 3) Cl                                                                              CHO OCH.sub.3                                                                         H  NHCOCH.sub.3                                                                           H OC.sub.4 H.sub.9                                                                      blue                                    19 CN Cl                                                                              CHO OCH.sub.3                                                                         H  NHCOCH.sub.3                                                                           H Cl      greenish                                                                      blue                                    __________________________________________________________________________     1) CH = C(CN).sub.2                                                           2) CH = C(CN)CO.sub.2 C.sub.4 H.sub.9                                         3) CO.sub.2 C.sub.2 H.sub. 5                                             

EXAMPLE 20

9.18 g of 2-amino-4-chloro-3,5-dicyanothiophene were introduced into amixture of 120 ml of 3:1 v/v of glacial acetic acid/propionic acid and20 ml of 85% strength by weight of sulfuric acid. 17.3 g ofnitrosylsulfuric acid (11.5% of N₂ O₃) were added dropwise at 0°-5° C.,and the mixture was stirred at that temperature for 3 hours.

The diazonium salt solution was added dropwise at 0°-5° C. to a mixtureof 16 g of N-(2-hydroxy-4-oxaoctyl)-2-methoxy-5-acetylaminoaniline in 50ml of N,N-dimethylformamide, 100 ml of water, 20 ml of dilutehydrochloric acid, 0.5 g of sulfamic acid and 300 g of ice. After 2hours at 0°-5° C., the mixture was worked up, and the dye was filteredoff with suction, washed neutral and dried. This gave 16.6 g of the dyeof the formula ##STR7## which dyes polyester in greenish blue shadeswhich are fast to light and dry heat setting and pleating.

The same method was used to obtain the dyes of the formula ##STR8##listed in the following Table 2:

                                      TABLE 2                                     __________________________________________________________________________    Ex.                                                                           No.                                                                              X  Y Z   R.sup.1                                                                           R.sup.2                                                                          R.sup.4  R.sup.5                                                                         R.sup.6 Hue on PES                              __________________________________________________________________________    21 CN Cl                                                                              CN  OCH.sub.3                                                                         H  NHCOC.sub.2 H.sub.5                                                                    H OC.sub.2 H.sub.5                                                                      greenish                                                                      blue                                    22 CN Cl                                                                              CN  OC.sub.2 H.sub.5                                                                  H  NHCOCH.sub.3                                                                           H OC.sub.4 H.sub.9                                                                      greenish                                                                      blue                                    23 CN Cl                                                                              CN  OCH.sub.3                                                                         H  NHCOCH.sub.3                                                                           H OCH.sub.3                                                                             greenish                                                                      blue                                    24 CN Cl                                                                              CN  OCH.sub.3                                                                         H  NHCOCH.sub.3                                                                           H OC.sub.6 H.sub.5                                                                      greenish                                                                      blue                                    25 CN Cl                                                                              CN  OCH.sub.3                                                                         H  NHCOCH.sub.3                                                                           H OH      greenish                                                                      blue                                    26 CN Cl                                                                              CN  OCH.sub.3                                                                         H  NHCOCH.sub.3                                                                           H OC.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                     greenish                                                                      blue                                    27 CN Cl                                                                              CN  OCH.sub.3                                                                         H  NHCOCH.sub.3                                                                           H OCH.sub.3                                                                             greenish                                                                      blue                                    28 CN Br                                                                              CN  OCH.sub.3                                                                         H  NHCOCH.sub.3                                                                           H OC.sub.4 H.sub.9                                                                      greenish                                                                      blue                                    29 CN Cl                                                                              CN  OC.sub.2 H.sub.5                                                                  H  NHCOC.sub.2 H.sub. 5                                                                   H OC.sub.4 H.sub.9                                                                      greenish                                                                      blue                                    30 CN Cl                                                                              CN  OCH.sub.3                                                                         H  NHCOC.sub.2 H.sub.5                                                                    H OC.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                     greenish                                                                      blue                                    31 CN Cl                                                                              CN  OCH.sub.3                                                                         H  NHCOCH.sub.2 OCH.sub.3                                                                 H OH      greenish                                                                      blue                                    32 CN Cl                                                                              CN  OCH.sub.3                                                                         H  NHCOC.sub.6 H.sub.5                                                                    H OC.sub.4 H.sub.9                                                                      greenish                                                                      blue                                    33 CN Cl                                                                              CN  OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                  NHCOCH.sub.3                                                                           H OC.sub.4 H.sub.9                                                                      greenish                                                                      blue                                    34 CN Cl                                                                              CN  OCH.sub.3                                                                         C.sub.4 H.sub.9                                                                  NHCOCH.sub.3                                                                           H OC.sub.2 H.sub.5                                                                      greenish                                                                      blue                                    35 CN Cl                                                                              NO.sub.2                                                                          OCH.sub.3                                                                         H  NHCOCH.sub.3                                                                           H OC.sub.4 H.sub.9                                                                      green                                   36 CN Cl                                                                              NO.sub.2                                                                          OCH.sub.3                                                                         H  NHCOCH.sub.3                                                                           H OC.sub.4 H.sub.9                                                                      green                                   37 1) Cl                                                                              CN  OCH.sub.3                                                                         H  NHCOCH.sub.3                                                                           H OC.sub.4 H.sub.9                                                                      blue                                    38 CN Cl                                                                              CN  OCH.sub.3                                                                         H  NHCOCH.sub.3                                                                           H Cl      greenish                                                                      blue                                    __________________________________________________________________________     1) CO.sub.2 C.sub.2 H.sub.5                                              

EXAMPLE 39

2.54 g of the dye described in Example 1 were admixed in 20 ml ofN,N-dimethylformamide with 1.02 g of acetic anhydride and 0.30 g of drysodium acetate, and the mixture was heated at 65° C. for 2 hours.

After cooling down to 25° C., the mixture was poured onto 200 ml ofice-water and worked up.

This gave 2.2 g of the dye of the formula ##STR9## which dyes polyesterin greenish shades having good all round fastness properties.

The same method was used to obtain the dyes of the formula ##STR10##listed in the following Table 3:

                                      TABLE 3                                     __________________________________________________________________________    Ex.                                                                           No.                                                                              X  Y Z   R.sup.1                                                                           R.sup.2                                                                          R.sup.4 R.sup.5                                                                             R.sup.6                                                                            Hue on PES                              __________________________________________________________________________    40 CN Cl                                                                              CHO OCH.sub.3                                                                         H  NHCOCH.sub.3                                                                          COC.sub.2 H.sub.5                                                                   OC.sub.4 H.sub.9                                                                   greenish                                                                      blue                                    41 CN Cl                                                                              CHO OCH.sub.3                                                                         H  NHCOCH.sub.3                                                                          COC.sub.4 H.sub.9                                                                   OC.sub.4 H.sub.9                                                                   greenish                                                                      blue                                    42 CN Cl                                                                              CHO OCH.sub.3                                                                         H  NHCOCH.sub.3                                                                          COC.sub.6 H.sub.13                                                                  OCH.sub.3                                                                          greenish                                                                      blue                                    43 CN Cl                                                                              CHO OCH.sub.3                                                                         H  NHCOCH.sub.3                                                                          CO.sub.2 C.sub.2 H.sub.5                                                            OC.sub.2 H.sub.5                                                                   greenish                                                                      blue                                    44 CN Cl                                                                              CHO OCH.sub.3                                                                         H  NHCOCH.sub.2 H.sub.5                                                                  1)    OC.sub.6 H.sub.5                                                                   greenish                                                                      blue                                    45 CN Cl                                                                              CHO OCH.sub.3                                                                         H  NHCOCH.sub.3                                                                          2)    OC.sub.4 H.sub.9                                                                   greenish                                                                      blue                                    46 CN Cl                                                                              CHO OC.sub.2 H.sub.5                                                                  H  NHCOCH.sub.3                                                                          COC.sub.3 H.sub.7                                                                   OCH.sub.3                                                                          greenish                                                                      blue                                    47 CN Br                                                                              CHO OCH.sub.3                                                                         H  NHCOCH.sub.3                                                                          COCH.sub.3                                                                          OC.sub.2 H.sub. 5                                                                  greenish                                                                      blue                                    48 3) Cl                                                                              CHO OCH.sub.3                                                                         H  NHCOCH.sub.3                                                                          COCH.sub.3                                                                          OC.sub.4 H.sub.9                                                                   blue                                    49 CN Cl                                                                              CN  OCH.sub.3                                                                         H  NHCOCH.sub.3                                                                          COC.sub.2 H.sub.5                                                                   OCH.sub.3                                                                          greenish                                                                      blue                                    50 CN Cl                                                                              CN  OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                  NHCOCH.sub.3                                                                          COC.sub.5 H.sub.11                                                                  OCH.sub.3                                                                          greenish                                __________________________________________________________________________     1) COC.sub.2 H.sub.4 OCH.sub.3                                                2) CON(C.sub.2 H.sub.5).sub.2                                                 3) CO.sub.2 Et                                                           

We claim:
 1. A thiopheneazo dye of formula I ##STR11## wherein X iscyano,Y is halogen, hydroxyl, mercapto, unsubstituted orphenyl-substituted C₁ -C₆ -alkoxy, C₅ -C₇ -cycloalkoxy, substituted orunsubstituted phenoxy, unsubstituted or phenyl-substituted C₁ -C₆-alkylthio, C₅ -C₇ -cycloalkylthio, phenylthio, chlorophenylthio, C₁ -C₆-alkylsulfonyl, phenylsulfonyl or methylphenylsulfonyl, is nitro, cyano,C₁ -C₄ -alkanoyl, benzoyl, C₁ -C₄ -alkylsulfonyl, phenylsulfonyl or aradical of the formula --CH═CB¹ B² or --CH═N--B³, in which B¹ and B² areidentical or different and each independently of the other is cyano, C₁-C₆ -alkoxycarbonyl whose alkyl chain may be interrupted by one or twooxygen atoms, or C₃ -C₆ -alkenyloxycarbonyl or one of B¹ and B² is cyanoand the other is C₁ -C₄ -alkylsulfonyl, substituted or unsubstitutedphenyl, benzoyl, phenylsulfonyl or carbamoyl and B³ is hydroxyl, C₁ -C₄-alkoxy, phenoxy or phenylamino R¹ is C₁ -C₄ -alkoxy, R² is hydrogen, C₁-C₁₀ -alkyl which may be interrupted by one or two oxygen atoms, or R³,R³ is radical of the formula CH₂ --CH(OR⁵)--CH₂ R⁶ and R⁴ isunsubstituted or hydroxyl-, C₁ -C₄ -alkoxy-, phenoxy-, chlorine- or C₁-C₄ -alkanoyloxy-substituted C₁ -C₆ -alkanoylamino, benzoylamino, orbenzoylamino substituted by methoxy, methyl or chloro, R⁵ is hydrogen,C₁ -C₁₀ -alkanoyl, C₁ -C₁₀ -alkoxycarbonyl or C₁ -C₁₀ -mono- ordialkyl-carbamoyl, the alkyl groups of said substituents beinguninterrupted or interrupted by one or two oxygen atoms, and R⁶ ischlorine, bromine, hydroxyl, phenoxy, allyloxy, C₁ -C₁₀ -alkoxy whichmay be interrupted by one or two oxygen atoms or substituted byhydroxyl, phenoxy, phenyl, C₁ -C₈ -alkanoyloxy, chlorine, bromine orcyano, C₁ -C₆ -alkanoyloxy, C₁ -C₆ -mono- or -dialkyl- aminocarbonyloxyor phenylaminocarbonyloxy and the substituents on substituted phenyl areindependently selected from the group consisting of C₁ -C₄ -alkyl, C₁-C₄ -alkoxy and halogen, and the substituents on substituted phenoxy aremethyl, isopropyl, methoxy or bromo.
 2. A thiopheneazo dye as claimed inclaim 1, whereinX is cyano, Y is halogen, C₁ -C₄ -alkoxy, phenylthio orphenylsulfonyl, Z is cyano, formyl or a radical of the formula --CH═CB¹B², in which B¹ is cyano and B² is cyano or C₁ -C₄ -alkoxycarbonyl, R¹is C₁ -C₄ -alkoxy, R² is hydrogen or C₁ -C₄ -alkyl, R³ is a radical ofthe formula --CH₂ --CH(OR⁵)--CH₂ R⁶ and R⁴ is C₁ -C₄ -alkanoylamino, R⁵is hydrogen or C₁ -C₄ -alkanoyl and R⁶ is chlorine, bromine, hydroxy,phenoxy, allyloxy, C₁ -C₄ -alkoxy or C₁ -C₄ -alkanoyloxy.